Polyester resin-cured laminate and method of preparing

ABSTRACT

A method of preparing a polyester resin composition laminate, which method comprises spraying an unsaturated polyester resin composition with an acrylic-urethane prepolymer onto a substrate, like a glass fiber, and curing the sprayed composition by radiant light.

REFERENCE TO PRIOR APPLICATIONS

This application is a divisional application of U.S. Ser. No.08/965,713, filed Nov. 7, 1997 now U.S. Pat. No. 6,037,385, which is adivisional application of U.S. Ser. No. 08/713,177, filed Sep. 12, 1996,now U.S. Pat. No. 5,747,552, issued May 5, 1998, which, is acontinuation-in-part of U.S. Pat. application Ser. No. 08/629,894 filedApr. 10, 1996 now U.S. Pat. No. 5,739,240, issued Apr. 14, 1998.

BACKGROUND OF THE INVENTION

Unsaturated polyester resins are polycondensation products of adicarboxylic acid with dihydroxy alcohols. Such polyester resinscatalyze to cure or harden, generally at room temperatures, to make awide variety of products. Unsaturated polyester resins are widely usedtoday to make products for use in the marine, transportation andbuilding industries, and in particular, fiber or particulate reinforcedproducts, such as glass fiber reinforced laminate-type products.Unsaturated polyester resins generally contain ethylenic unsaturationintroduced by the employment of unsaturated diacids, thus comprisingthermosetting-type resins. As such, unsaturated resins generally employmaleic and fumaric unsaturated acids, although saturated acids, phthalicand adipic acid may also be included to control or reduce the amount ofunsaturation in the final unsaturated polyester resin and to control thephysical properties. Dihydroxy alcohols most generally used aretypically ethylene, propylene, diethylene and dipropylene glycols.Cross-linking agents may be employed with the unsaturated polyesterresins. Generally, styrene monomers and diallyl phthalate are the mostcommon crosslinking agents. The styrene monomers are used to reduce theviscosity of the polyester resin and to act also as a cross-linker inthe polyester resins.

It is desirable, particularly in view of the toxicity of the styrenemonomer and government regulations, to reduce the concentration levelsof the styrene monomer from the usual 40% to 50% by weight of thepolyester resin to below 35% or 30% by weight. However, reductions instyrene monomer concentrations present problems in the polyester resinswith the increased viscosity of the resin, causing difficulties inapplying the resins, such as causing spray problems and glass roll-outwhen the resin is sprayed or used in conjunction with glass fibers. Thereduced styrene monomer polyester resin does not wet the glass inpreparing glass fiber laminates, and therefore, the surface of thesprayed glass fiber polyester resin typically must be contacted with aroller to prevent glass fibers from sticking out of the surface. Inaddition, the physical properties of the styrene monomer-reducedpolyester resins are also greatly reduced without the use of additional,supplemental cross-linkers in the polyester resin. The aromatic natureof styrene monomers in the unsaturated polyols improves the hydrolyticstability and increases the chemical resistance to water, detergents andcorrosion in the final, cured polyester resin product.

Acrylic monomers, such as methyl methacrylate (MMA) have been added tolow or reduced styrene monomer polyester resins for marine grade gelcoats and for outdoor applications. However, and unfortunately, MMA hasa strong odor, is a skin and eye irritant and results in a slowing ofthe cure rate of a polyester resin. However, such acrylic monomersusually improve UV, water and chemical resistance. Therefore, it is notdesirable to substitute MMA monomer for the styrene monomer or to add itwith the styrene monomer, since MMA is also a hazardous material.

It is therefore desirable to provide new and improved, photoinitiated,cross-linkable resin compositions to replace or reduce styrene monomerin unsaturated resins, to provide unsaturated, cured resins with betterphysical and chemical properties and to provide an unsaturated polyesterresin composition having reduced styrene monomer therein.

SUMMARY OF THE INVENTION

The invention relates to a modified acrylic urethane prepolymerconcentrate for use and admixture with radiation curable, unsaturatedpolyester resin compositions and to the unsaturated resin compositionscontaining the concentrate as a diluent and a cross-linking compositionand to the photocured unsaturated polyester resin compositions and theiruses in and the method of preparing laminates and resin products.

The invention concerns an improved, liquid modified, acrylic urethaneprepolymer concentrate adapted for addition to unsaturated resincompositions to provide improved cured resin properties and to provideunsaturated polyester resin compositions of reduced styrene monomercontent. The liquid concentration comprises a modified acrylic urethaneprepolymer or oligomer prepared by the reaction of a polyisocyanate,such as an aromatic isocyanate, like MDI (methylene di-p-phenyleneisocyanate) or an aliphatic isocyanate, usually in a stoichiometricamount or in a slight excess, with a hydroxyl-containing acrylatemonomer with or without the presence of a catalyst and a diluentmonomer, like a styrene monomer, generally in an amount of less than 40%by weight of the unsaturated polyester resin composition to which theconcentrate is added, and an inhibitor, such as a quinone compound, suchas benzoquinone, to retard any prereaction of the prepolymer and thestyrene monomer in the concentrate.

The invention is also concerned with unsaturated resin compositionssubject to curing in the presence of a catalyst, typically a peroxidealone or with a metal promoter, like a metal carboxylate, such as acobalt or copper salt, alone or in combination with variousaccelerators, which are amine or amide accelerators. The catalyticamount of the peroxide compound added just prior to use with the resincomposition contains a promoting amount of a metal promoter salt at roomtemperatures in order to provide sufficient exothermic heat to cure theunsaturated polyester resin composition containing the concentrate. Anunsaturated polyester resin composition is usually employed either aloneor typically in conjunction with filler material, such as particles orfiber materials, like clay, quartz, sand, limestone, mica, pigments orfibers, like glass fibers, and in some cases flame retardants likealuminum trihydrate, viscosity control agents and modifiers like formedsilica and flow control agents, or combinations in amounts of about 0%to 30% by weight of the resin in order to prepare cured laminates of theunsaturated polyester resin, such as a spray laminate, containing glassfibers admixed with the polyester resin.

It has been found further that the resin composition of the inventionmay be cured either alone by photoinitiation or in combination with aperoxide promoter where a dual curing reaction is desired. Theemployment of radiation compounds by the use of one or morephotoinitiators added to the prepolymer used with an unsaturated resinor to the prepolymer (oligomer) concentrate-unsaturated resincomposition provides many advantages in the shelf life, storage,handling and processing of the composition and in the resultantradiation cured resin and resin products produced thereby.

The photoinitiators employed may vary, depending on the intensity andtype of radiation to be used, and typically are selected to promote orinitiate the curing-polymerization reaction of the composition, such asby the generation of free radicals. The radiant energy employed mayinclude high energy radiation beams, but more particularly includevisible light (sunlight) or UV light. The selection of thephotoinitiator is usually based on the optimum absorption surges, e.g,250 to 450 nm or to which the curable composition either as centering ormolded product is to be exposed. The photoinitiator should be compatiblewith and admix with the prepolymer-oligomer concentrate and the resincomposition.

The photoinitiators are used in a sufficient amount to initiate andpromote polymerization, which amount may vary depending on the numberand type of photoinitiators and whether the composition also containschemical curing agents and promotion and the material used in thecomposition, the thickness of the composition and the radiant energy tobe used.

For example, the photoinitiator may be used in amounts of from about0.01 to 5.0 percent by weight of the unstructured resin composition,such as 1.5 to 3.0 percent by weight.

The photoinitiators may be used alone or in various combinations andgenerally are organic compounds like, but not limited to benzoins,ketals, ketones, phenones, and thioxanthones, and benzoates. Typicalspecific photometric compounds are: benzildimethyl ketal, 60% solutionof benzildimethyl ketal, mixture of benzoin normal butyl ethers,trimethylbenzophenone blend, alpha hydroxy ketone, blend oftrimethylbenzophenone blend and alpha hydroxy ketone,isopropylthioxanthone, blend of isopropylthioxanthone andtrimethylbenzophenone blend, ethyl 4-(dimethylamino)benzoate, andbenzophenone.

It has been discovered that acrylic urethane oligomers made by reactingpentaerythriol triacrylate and either MDI or HDI hexamethylenedi-isocyanate adducts provide improved physical properties and cycletime in unsaturated polyester resins. These hybrid resins, as described,are catalyzed using MEKP (methyl ethyl ketone peroxide) and promotedwith cobalt octoate (12%) and DMAA (Dimethyl Aceto Acetamide).

It has now been discovered that these peroxide cured resin hybrids cannow be cured using photoinitiators (PI) and radiant energy, such as UVor visible light, e.g. 365-450 nanometers. For PI compositions, cycletimes can be reduced to 2-3 minutes at 50-120 mils in thickness and upto 50% glass reinforcement. However, glass reinforcement is notnecessary when used as a coating.

It has been found that the photoinitiating curable prepolymer-resincomposition will provide many and significant advantages over theperoxide-curable prepolymer-resin composition. One advantage is theincreased shelf or container life of the PI composition, since once inthe container and free of radiant energy, a significant increase inshelf and container life is possible over the peroxide-containingprepolymer resin compositions, which are subject to low reaction overtime. Thus, the PI compositions may be stored for long periods and arequickly ready for use. Another advantage is that the PI compositions,particularly where used in enclosed areas, have an absence of anyperoxide or promoter odor. Also, the PI curable compositions often haveimproved physical properties over the peroxide curable prepolymer resincompositions and exhibit better processing properties as regards tocuring and cycle time. For example, where conventional unsaturatedpolyester resin compositions often take one to two hours or more to cureand the peroxide-curable prepolymer-resin compositions have reduced cureand cycle times, for example, of as low as five minutes, the PI curablecompositions provide cycle times generally of less than about fiveminutes, such as reduced to 1-3 minutes, and coating thicknesses ofabout 50 to 120 mils. The PI curable compositions permit complete curesin reduced time, and therefore promote mold efficiencies, since themolded products have been partially cured by radiant energy, and may berapidly demolded from the mold without waiting for the full cure to takeplace, as in the peroxide-curing compositions.

The curable prepolymer-resin compositions may be employed with flowmodifying agents such as wetting agents, which wet the surface to whichthe curable composition is to be applied, either in a mold or by spray,and to prevent or reduce the development of “fish eyes” or otherdeformations in the cured resin surface. It has also been discoveredthat the PI curable compositions can contain significant amounts of, forexample, up to about 15% by weight of particulate flame-retardantmaterials, such as, but not limited to, aluminum trihydrate, and stillbe effectively cured by the exposure of the curable composition toradiant energy, thus providing a relatively inexpensive, flameretardant, cured resin product. The PI-curable compositions may alsocontain minor amounts, as desired, for example, 1-20% or more by weight,of light-reflective materials, such as metal, for example, aluminumparticles, glitter and flakes, which provide further disseminating ofthe radiant energy throughout the curable composition, and increases theefficiency of the time of the radiant cure, and provides a metallic orglitter-looking cured resin surface, for example, for the use on such asboats, or in traffic marking lanes or traffic or other road signs. Wherethe prepolymer-resin composition is to be employed on a vertical orsloping surface such as in a spraying or coating operation, it is oftendesirable to add a viscosity-modifying amount of a viscosity-modifyingagent to the curable composition to prevent resin flow on the surfaceprior to cure, especially by the employment of various selected fixativecompositions, for example, but not limited to, fumed silica, in theamount of 0.01 to 5% by weight of the curable composition.

It has been discovered that the replacement or reduction in amount of astyrene monomer as a diluent and cross-linking additive to unsaturatedpolyester resin compositions may be accomplished by employment ofmodified acrylic urethane prepolymers which result in improvedproperties to the cured polyester, better handling in preparinglaminates as regards to roll-out of the laminate, and permits reductionof the styrene monomer, typically to amounts lower than 40%, for examplefrom 0% to 30% by weight of the polyester resin composition.Particularly, it has been discovered that higher functionality acrylicmonomers improve the polyester properties of the cured polyestercomposition. When a polyisocyanate, like MDI, is added to unsaturatedpolyester resin compositions by itself, such MDI tends to react with thehydroxyl group unsaturated polyester resin composition leading toincreased and high viscosity which greatly reduces the feasibility ofemploying the unsaturated polyester resin composition. Employment of aMMA monomer itself provides certain disadvantages. Therefore, theemployment of a modified acrylic urethane prepolymer, a liquidconcentrate, either alone or together with a styrene monomer and aninhibitro, may be used as a diluent additive to unsaturated polyesterresin compositions to improve properties and to prepare compositions ofreduced styrene monomer content.

In particular, it has been discovered that the high functionalityaliphatic urethane prepolymers provide for a variety of improved cureproperties of a polyester resin as set forth, for example, in Table I.

TABLE I Properties Mono  Di  Tri  Tetra  Penta Cure Speed Slow→ → → → →→ → → → → → → → → → Fast Flexibility High← ← ← ← ← ← ← ← ← ← ← ← ← ← ←Low Hardness Low→ → → → → → → → → → → → → → → →High Solvent ResistanceLow→ → → → → → → → → → → → → → → →High Cross-link Density Low→ → → → → →→ → → → → → → → → →High

The employment of a special hydroxyl containing high functionalityacrylic monomer, that is, an acrylic monomer with hydroxyl groups, beingmade into a prepolymer by the employment of a polyisocyanate, eitheraromatic or aliphatic diisocyanate, and which prepolymer so prepared ina preferred embodiment remains in a liquid condition. This liquidconcentrate can be added to the low level styrene monomer unsaturatedpolyester resin compositions and produces a stable polyester resincomposition, which does not react unless and until the peroxidecatalysts or a catalyst-accelerator promoter combination is added to theunsaturated polyester resin composition. The addition of the catalyticcuring composition, such as the use of methyl ethyl ketone peroxide asone example, provides for rapid cure of the polyester withoutsignificant loss of unreacted styrene monomer, so that the resultingunsaturated polyester resin with the liquid concentrate wets glass fiberwith excellent efficiency and significantly reducing the need toroll-out the glass, where the unsaturated polyester resin composition issprayed with glass fibers to form a glass fiber reinforced laminate.

The concentrate includes in one example a hydroxyl alkyl, such C₂-C₆acrylic monomer, which is reacted with a diisocyanate to provide themodified acrylic urethane prepolymer for use in the concentrate. Lowfunctionality acrylic monomers, while not the preferred embodiment,provide for improved cure, chemical and physical properties of thepolyester resin, since such low functionality modified acrylic urethaneprepolymers with the low functionality used therein provide forsolidified prepolymers or prepolymers which rapidly gel, and a liquidconcentrate is the preferred embodiment. Some representative types ofthe acrylic monomers useful in the invention would include 2-hydroxyethyl acrylate; hydroxy propyl acrylate; 2-hydroxy ethyl methacrylate;2-hydroxy ethyl propyl methacrylate; and acrylic urethane prepolymersmade from having an 100 index down to a 20 index with solidificationoccurring in most prepolymers, except for the prepolymers having a 20 orbelow index.

A preferred acrylic polymer which provides for a liquid concentratecomprises a pentaerythritol acrylate composed of tri-, tetra- andpentacrylate, which acrylic monomer has an hydroxyl group or an activehydrogen for reaction with the diisocyanate. Reaction of thispentaerythritol polyacrylate with diisocyanate, such as MDI, atdifferent levels produces a stable liquid prepolymer, which does notreact when added to an unsaturated polyester resin prior to the peroxideagent addition to or exposure to radiation of the promoted unsaturatedresin.

Other high functionality hydroxyl acrylic monomers suitable for usewould include ethoxylated or propoxylated trimethylol propane orglycerol polyacrylate, e.g., tri acrylate monomers. Specific highfunctionality acrylic monomers suitable for use include ethoxylatedtrimethylol propane triacrylate; pentaerythritol tri, tetra andpentaacrylate, propoxylated trimethylolpropane triacrylate; propoxylatedglycerol triacrylate; di-tri methylol propane tetracrylate;dipentaerythritol pentacrylate; and ethoxylated pentaerythritoltetracrylate and combinations thereof.

The prepolymer is made by reacting with or without a catalyst thehydroxyl-containing acrylic monomer with polyisocyanate, moreparticularly, an aliphatic or aromatic diisocyanate, such as, but notlimited to an aromatic diisocyanate, like MDI, or an aliphaticisocyanate, such as trimerized HDI (hexamethylene diisocyanate) ortrimerized IPDI (isophenyl diisocyanate), or other acceptablediisocyantes or prepolymers which will react with the hydroxyl groups inthe acrylic monomer. The compound, pentaerythritol triacrylate is acommercial product known as SR 444 of Sartomer Company, Inc. of Exton,Pa.

The prepolymer is added to an unsaturated resin composition, eitheralone or preferably in the concentrate form, known to contain somestyrene monomer for viscosity control purposes, and thereby needing areduction of the styrene monomer employed in the unsaturated polyesterresin. The total amount of styrene monomer in the unsaturated resincomposition would be less than 30% by weight. The prepolymer concentratewould also generally contain an inhibiting agent to provide for storagestability of the liquid concentrate, such as to maintain at leasttwo-weeks' stability at 120° F., and which inhibitor generally comprisesa quinone compound, such as parabenzonequinone.

The prepolymer concentrate is employed as an additive and as a diluentto unsaturated polyester resin compositions, such as those unsaturatedresin compositions, but not limited to polyester resins prepared by thereaction of propylene glycol with maleic acid anhydride; and thereaction of isophthalic acid-maleic anhydride with neo pentyl glycol, orother known unsaturated polyester resin compositions.

Generally, the unsaturated resin compositions contain an inhibitor toprevent prereaction until a promoter or catalyst is added to effect curein the polyester resin after the addition of the prepolymer concentrate.The unsaturated polyester resin compositions contain a monomer forcross-linking therewith, such as a diluent styrene monomer at reducedlevels, where a concentrate prepolymer is employed. A cure is effectedby employing an organic peroxide compound, and typically a metal salt,such as a fatty acid salt, like a cobalt octoate or potassium octoate,is employed in combination with an organic ketone, such as methyl ethylketone peroxide, to provide for an exothermic curing reaction. Thepromoter and catalyst composition may also contain amide-type compoundsfor acceleration purposes, such as the dimethyl acetamide. Generally,the peroxide, metals salts, amines and amides are employed at low levelswith the peroxide employed from about 0.1% to 2.5% by weight and themetal salts ranging from about 0.05% to 0.5% by weight and the amine oramide from about 0.05% to about 0.5% by weight. It has been found thatafter addition of the concentrate prepolymer to the unsaturatedpolyester resin composition used to prepare laminates, that the roll-outtime was reduced, for example, to less than five minutes. The polyesterresin composition without the concentrate prepolymer, even though suchcomposition gelled in ten minutes, tended to stay rubbery for fiveminutes or more until a peak exotherm occurred, while with the use ofthe concentrate prepolymer, cure of the polyester resins to a rigidphysical condition occurred in less than five minutes.

It has been found that the employment of the prepolymer concentrate ofthe invention helps in reducing roll-out where the unsaturated resincomposition is employed with fiberglass, such as in a spray or moldoperation, so that in the preparation of cured polyester fiberglasslaminates with the use of the liquid concentrate prepolymer, no rollingof the concentrate was required when the concentrate was employed.Further, it has been noted that the polyester resin systems, with theliquid prepolymer concentrate added thereto, had little or no styrenemonomer smell within three to four minutes after the spraying of theresin composition, which is believed to occur as a result of the crosslinking taking place and tying up the styrene monomer.

The invention will be described for the purposes of illustration only inconnection with certain embodiments; however, it is recognized thatthose persons skilled in the art may make various modifications,changes, additions and improvements to the illustrated embodiments,without departing from the spirit and scope of the invention.

EMBODIMENTS OF THE INVENTION Example 1

A liquid concentrate prepolymer prepared by admixing together 500 partsper weight of pentaerythritol triacrylate (acrylate SR-444) and 100parts per weight of MDI (Papi 94, a trademark of Dow Chemical Company)and slowly reacted together without the presence of catalyst to providea liquid pentaerythritol acrylic urethane. Four hundred parts per weightof a styrene monomer were added to the liquid prepolymer and togetherwith 50 ppm of an inhibitor, parabenzoquinone. Employment of straighturetonomini-isocyanate (like Dow L143) and polymeric MDI (like Papi 27)were also employed with the acrylate SR-444. Prepolymer solidificationtook place while heating the mixture in the oven. Low functionalityhydroxyl-containing acrylates were tried employing diisocyanates ofPapi-94 (Dow L143 and Papi 27); however, all these low functionalitymonomers solidified when the prepolymers were made.

Example 2

The liquid prepolymer concentrate was added to different types ofunsaturated polyester resins, such as a general purpose orthophthalicresin containing 30% styrene monomer and NPG glycol (a registeredtrademark of Eastman Chemical Products Inc. for neopentyl glycol)orthoresin containing 30% styrene monomer, an NPG isophthalic resincontaining 30% styrene monomer and DCPD ortho resin blends containing30% styrene monomer. The unsaturated resin composition contained 50 ppmof an hydroquinone inhibitor with the mixing in of the liquid prepolymerconcentrate, catalysts and promoters were admixed as follows: 2%catalyst of methyl ethyl ketone peroxide (containing 9% oxygen); 0.2parts per weight of 12% cobalt octuate as a promoter; 0.2 parts perweight of dimethyl acetyl acetamide (DMAA); and 0.1 parts per weight ofpotassium octuate (15%). Ten percent of the liquid prepolymerconcentrate was added to each resin. Gel time without the concentratewas about 10 minutes, while with the concentrate added, gel time wasreduced to 2.5 to 2.8 minutes. All samples prepared without theconcentrate, even though they gelled in ten minutes, stayed rubbery forfive minutes until a peak exotherm occurred, while the same polyesterresin samples with the 10t liquid prepolymer concentrate became rigid inless than five minutes.

Example 3

The unsaturated polyester resin samples containing the 10% liquidprepolymer concentrate were put on a Binks B-8 fiberglass spray machineand sprayed with a Binks Century gun with external mix catalyst aboveand the fiberglass at about 22% by weight was sprayed at ¾ inch fiberlength employing a four by four foot plate mold. With each unsaturatedpolyester resin system used without the liquid prepolymer concentrate onthe surface, the glass required rolling to make an acceptable laminatewithout air. The liquid prepolymer concentrate added at 10% and sprayedprovided for a fiberglass polyester cured laminate requiring no rollout. Further, the resin systems with the liquid concentrate had nostyrene monomer smell within three to four minutes of spraying of thepolyester resin as a result of cross-linking taking place with thestyrene monomer.

Physical testing was done on all the polyester resin compositions, withor without the liquid prepolymer concentrate as added at 10%, and thetest oligomers are shown on the accompanying Table II.

Example 4

Compression-molded fiberglass trays were prepared employing anisophthalic polyester resin with a heat-activated catalyst, such astertiary butyl perbenzoate, and added to a 33% glass fiber mat, withmold temperatures at 2800F., a cycle time of 90 seconds and with 10% ofthe liquid prepolymer concentrate added to the polyester resin. Uponaddition of the liquid prepolymer concentrate, cycle times for curingwere reducing to 60 seconds. The glass fiber wet-out was improved,styrene emissions were reduced and the laminate had improved physicalproperties and chemical resistance.

Example 5

Further tests were carried out with other polyester resins with andwithout a styrene monomer added and to which 10% by weight of the liquidconcentrate of Example 1 was added. The cycle times of the polyesterresin increased to 10 to 12 minutes on all types of polyester resins,and when each polyester resin system was sprayed with the fiberglass, noimprovement was seen over the same polyester resin without the presenceof the liquid prepolymer concentrate of the invention.

TABLE II Urethane Oliomers

Aliphatic urethane acrylate and 2-(2 Ethoxyethoxy) Ethyl acrylate ester(Craynor 961-H)

Epoxy acrylate oligomer plus 1, 6 Hexanediol diacrylate ester (Craynor120 B)

Aromatic urethane oligomer plus 1, 6 Hexanediol diacrylate ester(Craynor 970)

Example 6

In the marine and bathtub industry in the preparation of fiberglasslaminate, water absorption is critical to the success of the endproduct. Extensive boiling tests were run on samples of polyester resinsof DCPD, G.P.-Ortho, NPG-Ortho and NPG-Iso polyester resins, both withand without the liquid prepolymer concentrate added. The following TableIII shows the percent water absorption at 80° C. for 160 hours.

TABLE III Type Resin DCPD DCPD + C* PG PG + C NPG Orthophthalate +CNPG - Isophthalate + C % H₂O 3.2 1.6 3.1 1.4 2.9 1.4 2.0  1.2 Absorption*C = 10% concentrate made from SR-444.

The above results indicate that all unsaturated polyester resincompositions showed significant improvement in water absorption when theliquid prepolymer concentrate was added at a level of 10% parts byweight.

Thus, the modified prepolymer concentrate prepared by the employment ofpentaerythritol triacrylate, MDI and a styrene monomer with an inhibitorwhen added to unsaturated polyester resin compositions results inimprovement in the physical and chemical properties, such as decrease incure time, reduction in styrene emissions, reduction in styrene odorwhen sprayed, reduction in roll-out of molded or sprayed laminates,reduction in water absorption, increased chemical resistance, higherheat distortion temperatures and higher impact strength.

The unsaturated polyester resin composition with the modifiedacrylic-urethane prepolymer or oligomer and with a styrene monomer ofless than about 30% by weight may be cured with a methyl ethyl ketoneperoxide (1.5%-2.0%) and a cobalt salt (0.1%-0.5%). The composition canbe sprayed as a glass-fiber barrier coat behind a polyester orpolyester-acrylic gel coat with a very fast cure time and with rapidcure. The barrier coat strengthens the gel coat and reduces waterabsorption and lowers water and vapor transmission. The composition maybe sprayed or used with charged glass fibers in an open or closed mold,so that a no-roll surface without air entrapment can be prepared. Afterthe gel coat is applied and a barrier coat is added (prior to resin andglass application), no glass fibers are visible on the gel coat side,eliminating veil mats, to provide a class A finish where a class A moldis used.

Example 7

HP 1161 unsaturated polyester resin was used as a base material. Thisbase material is a NPG orthophthalic resin with 30% styrene monomer, anda 10% by weight acrylic oligomer made by reacting pentaerythritoltriacrylate and a low functionally MDI adduct and blended with 2% byweight of photoinitiator KB-1 (Benzil dimethyl ketal). No peroxide orpromoters were used. The PI containing composition material was appliedto a piece of wood at 50 mils thickness. The wood sample was takenoutside in sunlight. Cure time was two minutes with a tack free surface.Total cure and hardness occurred in five minutes.

The same composition was promoted using cobalt octoate 12% and DMAA atlevels of 0.1 and 0.3% respectively.

The PI promoted composition was coated on a wood sample at 50 milsthickness and placed outside. No difference in cure was seen. Thepromoted resin systems and photoinitiator was cured using 2% MEKP (925Norac 9% O₂).

A 3″ disc 120 mils thick was cast of the PI-promoted composition andcured in five minutes. This resin system was taken outside after beingapplied at 50 mils to a wood sample. The sample was cut in half and halfwas placed in direct sunlight and half in indirect light. Results showedthe direct sunlight sample cured in 2-3 minutes and the indirect lightsample cured in 10 minutes, but remained tacky at the surface. It iswell known that unsaturated polyester resins in their films usually haveparaffin wax added to prevent air inhibition. It is also known thatacrylic oligomers and monomers will not cure when exposed to air intheir films.

Example 8

The hybrid resin composition with its acrylic oligomers and thephotoinitiator was added to 50% glass cloth. Two glass plates were usedto contain the resin and glass to form a sandwich. The plates were takenoutside and exposed to direct sunlight, and after five minutes theplates were removed. A stiff tackfree resin-covered glass laminateresulted. It should be noted that no smell of styrene monomer waspresent.

The same resin composition with promoters and catalyzed with MEKP at 2%was added to 50% glass cloth. The sample was allowed to cure for fiveminutes and removed. The sample was rubbery and had a styrene monomerand peroxide smell. Ten minutes after the sample was removed, the samplewas cured and stiff.

The unsaturated polyester resin HP 1161 was tried without the acrylicoligomer. The photoinitiator was added at the same level, 50 mils wasadded on a wood sample. The sample was taken outside and exposed todirect sunlight. The sample cured in 12 minutes and remained sticky for20 minutes. The hardness was never reached when compared to the samematerial with the acrylic oligomer added.

A standard acrylic oligomer produced by Sartomer Company, Inc. of Exton,Pa., called CN 975 was tried. The material was cut in 1,6 hexanediacrylate to reduce the viscosity at a 60/40 ratio. Ten percent of theoligomer was added to 1164 resin with the photoinitiator. The sample wasplaced outside on the wood sample. Cure was quick but the surfaceremained wet for 30 minutes. Stickiness never disappeared.

The same standard oligomer from Sartomer, CN 975, was tried by itself.Two percent KP-1 PI was added at 50 mils to a wood sample. This samplewas exposed to direct sunlight. The sample did not cure on the surface,but did cure under the surface. The wetness did not go away.

It should be noted that the PI prepolymer-resin composition also cureswell when using 0.5 to 1 mils thickness and high intensity light on acommercial UV curable machine.

The new hybrid PI compositions, using HP 1161 resin and the specialoligomers (prepolymers), are a superior coating or laminating resin.

Example 9

The PI composition was spray applied at 50 mils thickness to concreteand asphalt surfaces. The hybrid PI composition cured in 2-3 minuteswith a beautiful high gloss coating. For vertical surfaces a 1-2% fumedsilica was added as a viscosity control agent. No differences in curewere seen.

CaCO₃ and aluminum trihydrate were tried at levels up to 50% in the PIhybrid composition in direct sunlight. The PI composition still curedrapidly without tackiness.

Example 10

The hybrid resin was sprayed as a gel coat 20 mils on a waxed fiberglassmold. The mold was exposed to direct sunlight for three minutes. The PIhybrid composition was put through a standard fiberglass machine where30% of 1″ chopped glass was added to the spray pattern. The PI resincomposition was sprayed 125 mils over the 20 mils coating. No rollingwas necessary, because of the low surface tension of the resincomposition. The mold was again taken outside and exposed to directsunlight. The sample was left for five minutes in the mold and removed.A cured fiberglass laminate was made without MEKP or styrene odor.

What is claimed is:
 1. A method of preparing a cured, unsaturated,polyester resin composition substrate, which method comprises: a)providing an unsaturated polyester resin composition prepared by thereaction of a dicarboxylic acid and a dihydroxy alcohol, and whichpolyester resin composition includes a cross-linking amount of across-linking monomer in an amount of less than 40% by weight of thecomposition and a photoinitiating amount of a photoinitiator; b) addingan additive amount of a liquid acrylate-urethane prepolymer to thepolyester resin composition, the prepolymer prepared by the reaction offree NCO groups of a polyisocyanate or polyisocyanate prepolymer with ahydroxy-functional acrylic monomer; c) applying the polyester resincomposition onto a substrate; and d) exposing the applied polyesterresin composition to photo radiation to promote curing of the polyesterresin composition.
 2. The method of claim 1 wherein the liquidprepolymer is prepared by the reaction of a polyisocyanate selected fromthe group consisting of: methylene di-p-phenylene isocyanate (MDI);hexamethylene diisocyanate (HDI); and isophenyl diisocyanate (IPDI) withthe acrylic monomer.
 3. The method of claim 1 wherein the acrylicmonomer comprises a polyerythritol acrylate.
 4. The method of claim 1wherein the cross-linking monomer is styrene or diallyl phthalate in anamount of less than about 30% by weight of the composition.
 5. Themethod of claim 1 which includes adding a peroxide catalyst to thecomposition and dual curing the composition with the peroxide catalystand the photoinitiator.
 6. The method of claim 1 which includes addingthe liquid prepolymer to the composition in an amount of 5 to 30 percentby weight of the composition.
 7. The method of claim 1 wherein theacrylic monomer comprises an ethoxylated or propoxylated acrylate. 8.The method of claim 1 which includes spraying the composition onto thesurface of a gel-coated substrate.
 9. The method of claim 1 whichincludes spraying the composition with glass fibers onto the substrate.10. The method of claim 1 which includes exposing the appliedcomposition to radiant energy in the range of about 250 to 450nanometers.
 11. The method of claim 1 which includes applying thecomposition to a glass cloth substrate.
 12. The method of claim 1 whichincludes: a) applying an unsaturated, polyester resin composition gelcoating onto a mold surface; b) spraying the composition with glassfibers onto the gel coating in the mold; and c) recovering the coatedsubstrate from the mold.
 13. The method of claim 1 which includesapplying the composition on a coating layer of about 50 to 120 mils, andwherein substantial curing occurs in less than about 3 minutes.
 14. Thephoto radiation-cured composition-laminate prepared by claim
 1. 15. Thephoto radiation-cured composition-laminate prepared by claim
 12. 16. Themethod claim 1 wherein the photoinitiator comprises from about 0.01 to5.0 percent by weight of the polyester resin composition.
 17. The methodof claim 1 wherein the polyester resin composition includes a viscositymodifying amount of 0.01 to 5 percent by weight of the composition ofsilica.
 18. The method of claim 1 which includes an inhibitor to providestorage stability to the polyester resin composition.
 19. The method ofclaim 1 which includes applying the polyester resin composition onto afiberglass-containing substrate in a mold.
 20. The method of claim 1wherein the polyisocyanate is a diisocyanate, the acrylic monomer is apentaerythritol triacrylate, and the cross-linking monomer is styrene.21. The method of claim 1 wherein the substrate comprises a glass fibermat on a mold to prepare a fiberglass tray.
 22. The method of claim 1which includes preparing the prepolymer by reacting a stoichiometric orexcess amount of the polyisocyanate with the acrylic monomer.
 23. Themethod of claim 1 wherein the acrylic monomer is selected from the groupconsisting of: 2-hydroxy ethyl acrylate; hydroxy propyl acrylate;2-hydroxy ethyl methacrylate; 2-hydroxy ethyl propyl methacrylate; andacrylic urethane prepolymers.
 24. The method of claim 1 wherein thepolyester resin composition comprises about 1 to 20 percent by weight oflight-reflective materials.